Method for producing ultra-thin tungsten layers with improved step coverage

ABSTRACT

A tungsten nucleation film is formed on a surface of a semiconductor substrate by alternatively providing to that surface, reducing gases and tungsten-containing gases. Each cycle of the method provides for one or more monolayers of the tungsten film. The film is conformal and has improved step coverage, even for a high aspect ratio contact hole.

CROSS-REFERENCE TO RELATED PATENT APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.13/633,502, filed Oct. 2, 2012, which is a continuation-in-part of U.S.patent application Ser. No. 13/095,734, filed Apr. 27, 2011 (now U.S.Pat. No. 8,409,985), which is a continuation of U.S. patent applicationSer. No. 12/030,645, (now U.S. Pat. No. 7,955,972), filed Feb. 13, 2008,which claims priority from U.S. Provisional Patent Application No.60/904,015, filed Feb. 27, 2007 and which is also a continuation-in-partof U.S. patent application Ser. No. 11/265,531, (now U.S. Pat. No.7,589,017), filed Nov. 1, 2005, which in turn is a continuation-in-partof U.S. patent application Ser. No. 10/815,560 (now U.S. Pat. No.7,262,125), filed Mar. 31, 2004, which in turn is a continuation-in-partof U.S. patent application Ser. No. 10/649,351 (now U.S. Pat. No.7,141,494), filed on Aug. 26, 2003, which is in turn acontinuation-in-part of U.S. patent application Ser. No. 09/975,074 (nowU.S. Pat. No. 6,635,965) filed Oct. 9, 2001, which in turn claimspriority from U.S. Provisional Patent Application No. 60/292,917, filedMay 22, 2001. All prior applications are incorporated herein byreference for all purposes.

FIELD OF THE INVENTION

The present invention relates to the chemical vapor deposition of atungsten film, and more particularly, to the nucleation of thatdeposition process on a semiconductor substrate.

BACKGROUND OF THE INVENTION

In Integrated Circuit (IC) manufacturing individual devices, such as thetransistors, are fabricated in the silicon substrate and then they areconnected together to perform the desired circuit functions. Thisconnection process is generally called “metallization”, and is performedusing a number of photolithographic patterning, etching, and depositionsteps.

The deposition of tungsten (W) films using chemical vapor deposition(CVD) techniques is an integral part of many semiconductor fabricationprocesses since it can produce low resistivity electrical connectionbetween i) adjacent metal layers (vias) and ii) first metal layer andthe devices on the silicon substrate (contact). Typically the W film isdeposited through the reduction of tungsten hexafluoride (WF₆) byhydrogen (H₂) or silane (SiH₄). In a typical tungsten process, the waferis heated to the process temperature in a vacuum chamber, and themsoaked in SiH₄ gas to protect the already deposited titanium liner thinfilm on the substrate from possible reaction with WF₆. A thin layer oftungsten film, known as the seed or nucleation layer, is deposited bythe reaction of WF₆ and SiH₄. Finally, the via or contact is filled withtungsten by the reaction of WF₆ and H₂ (“plugfill”).

Conventionally, the WF₆ and reducing gas (SiH₄ or H₂) are simultaneouslyintroduced into the reaction chamber. It is expected that in a tungstenprocess all vias and contacts are completely filled with tungstenmaterial, i.e., a 100% plugfill is achieved. The tungsten plugfillprocess is very sensitive to the conformality of the tungsten seed ornucleation layer in the vias and contacts.

The common problems associated with many seed layer depositiontechniques are poor sidewall step coverage and conformality. This meansthat the seed layer is much thicker in wide-open areas, such as on topof the contacts and vias as compared to the bottom and lower portion ofthe sidewalls of the contacts and vias. With the decrease of the designrule of semiconductor devices, the diameter of the contacts and vias getsmaller while their heights do not decrease. Thus, the aspect ratio(height divided by diameter) of contacts and vias keep increasing. Theincreased aspect ratio exacerbates the problem with the step coverageand conformality, thus degrading the quality of the plugfill process.

In a conventional CVD process, reactive gases arrive at the substratesimultaneously with film growth resulting from continuous chemicalreaction of the precursor and reactant gases on the substrate surface.Uniform and reproducible growth of the film is dependent on maintenanceof the correct precursor and reactant flux at the substrate. The growthrate is proportional to the precursor flux at the substrate and to thesubstrate temperature.

Atomic layer deposition (ALD) is a method of sequentially depositing aplurality of atomic layers on a semiconductor substrate by sequentiallyinjecting and removing reactants into and from a chamber. ALD is asurface controlled process and uses two-dimensional layer by layerdeposition. ALD uses a chemical reaction like CVD but it is differentfrom CVD in that reactant gases are individually injected in the form ofa pulse instead of simultaneously injecting reactant gases, so they arenot mixed in the chamber. For example, in a case of using gases A and B,gas A is first injected into a chamber and the molecules of gas A arechemically or physically adsorbed to the surface of a substrate, therebyforming an atomic layer of A. The gas A remaining in the chamber ispurged using an inert gas such as argon gas or nitrogen gas. Thereafter,the gas B is injected and chemically or physically adsorbed, therebyforming an atomic layer of B on the atomic layer of A. Reaction betweenthe atomic layer of A and the atomic layer of B occurs on the surface ofthe atomic layer of A only. For this reason, a superior step coveragecan be obtained regardless of the morphology of the substrate surface.After the reaction between A and B is completed, residuals of gas B andby products of the reaction are purged from the chamber. The process isrepeated for multiple layers of material to be deposited.

Thus, in contrast to the CVD process, ALD is performed in a cyclicfashion with sequential alternating pulses of the precursor, reactantand purge gases. The ALD precursor must have a self-limiting effect suchthat the precursor is adsorbed on the substrate in a monolayer atomicthickness. Because of the self-limiting effect, only one monolayer or asub-monolayer is deposited per operation cycle. ALD is conventionallyconducted at pressures less than 1 Torr.

Methods, which would form uniform seed layers in channel or vias andresult in an improvement in the subsequent filling of the channel orvias by conductive materials, has long been sought, but has eluded thoseskilled in the art.

SUMMARY OF THE INVENTION

The present invention provides a method of forming a tungsten nucleationlayer a surface of a semiconductor substrate. The method comprises thesteps of comprising the steps of: positioning said semiconductorsubstrate at a deposition station within a single or multi-stationdeposition chamber; heating said semiconductor substrate to atemperature between approximately 250 to 475° C. at said depositionstation; and performing an initiation soak step, which consists ofexposure of the substrate to a gas in a gaseous or plasma state forabout 2 to about 60 seconds. A reducing gas is subsequently flowed intothe deposition chamber whereby about one or more, preferably two ormore, and most preferably, three or more monolayers of reducing gas aredeposited onto the surface of the substrate. The deposition chamber isthen purged of the reducing gas and a tungsten-containing gas is flowedinto the chamber, whereby the deposited reducing gas is substantiallyreplaced by tungsten to provide the nucleation layer.

Preferably, the initiation soak gas comprises SiH₄, B₂H₆, Si₂H₆, H₂, Ar,N₂, or O₂, or a combination thereof and the soak gas is provided in agaseous or plasma state. The plasma state can be produced using aradiofrequency or microwave energy source.

In a preferred embodiment, the reducing gas comprises SiH₄, Si₂H₆, H₂.B₂H₆, or SiH₂Cl₂ or a combination thereof. The reducing gas may furthercomprise, argon, hydrogen, nitrogen, or a combination thereof.

Preferably, the tungsten-containing gas comprises WF₆, WCl₆, or W(CO)₆or a mixture thereof. The tungsten-containing gas may further compriseargon, hydrogen, nitrogen or a mixture thereof.

According to some embodiments, the method further comprises the step ofpurging the tungsten-containing gas from the chamber. Purging can beaccomplished through the introduction of a purge gas, such as hydrogen,nitrogen, an inert gas, or a mixture thereof. Alternatively, the gasesmay be evacuated from the chamber using a vacuum pump.

The method of the invention can be repeated until the desired thicknessof tungsten nucleation layer is obtained and/or may comprise furthersteps to produce a desired IC.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention may be better understood, and its numerousobjects, features, and advantages made apparent to those skilled in theart by referencing the accompanying drawings. For ease of understandingand simplicity, common numbering of elements within the illustrations isemployed where the element is the same between illustrations.

Panel A of FIG. 1 illustrates the relationship between nucleation layerfilm thickness and number of cycles at temperatures ranging from 150 to450° C. with dosing of 40 sccm of SiH₄ for 2 seconds and 600 sccm of WF₆for 2 seconds. Panel B of FIG. 1 shows the relationship between growthrate and number of cycles under similar process parameters.

FIG. 2 shows the relationship of surface roughness, measured inAngstroms with thickness of the pulsed nucleation layer for nucleationlayers produced by conventional CVD technology (large dark circles);pulsed nucleation technology at 350° C. (small dark circles); pulsednucleation technology at 250° C. (hollow circles) and a semiconductorsubstrate comprising CVD-TiN (100 Angstroms) on TEOS oxide (squares).

FIG. 3 depicts the relationship between growth or deposition rate (inAngstroms/second) and number of cycles for an embodiment of theinvention wherein continuous hydrogen delivery, at various pressures, isused in connection with the pulsed nucleation.

FIG. 4 shows a schematic representation of an embodiment of the dualdivert gas box.

FIG. 5 shows a schematic representation of a deposition station modulehaving a flush-mounted showerhead 501, a fully purged top plate 503, andan annular pumping port 509. Wafer 507 is surrounded by an inert gascurtain 505.

DETAILED DESCRIPTION OF THE INVENTION

Embodiments of the present invention will be described with reference tothe aforementioned figures. These figures are simplified for ease ofunderstanding and description of embodiments of the present inventiononly. Modifications, adaptations or variations of specific methods andor structures shown and discussed herein may become apparent to thoseskilled in the art. All such modifications, adaptations or variationsthat rely upon the teachings of the present invention, and through whichthese teachings have advanced the art, are considered to be within thespirit and scope of the present invention.

Overview

The present invention provides a method to form a conformal tungstennucleation layer by depositing a plurality of tungsten layers, each ofabout one or more monolayers in thickness, on a semiconductor substrateby sequentially injecting and removing reactants into and from achamber. According to one embodiment of the invention, the methodcomprises the steps of:

-   positioning the semiconductor substrate at a deposition station    within a deposition chamber;-   heating the semiconductor substrate to a temperature between    approximately 250 and 475° C., and preferably at about 350° C., at    the deposition station;-   performing an initiation soak step, which comprises exposure of the    substrate to a gas in a gaseous or plasma state for about 2-60    seconds to reduce or eliminate any nucleation delay;-   flowing a reducing gas into said deposition chamber whereby about    one or more monolayers of the reducing gas are deposited onto said    surface of said substrate;-   purging the reducing gas from the deposition chamber; and-   flowing a tungsten-containing gas into said deposition chamber,    whereby said deposited reducing gas is substantially replaced by    tungsten to provide said nucleation layer.

In a particularly preferred embodiment, the pressure of the depositionchamber is maintained at more than about 1 Torr. Preferably, two or moremonolayers and more preferably, three or more monolayers, of thereducing gas are deposited onto the surface of the substrate. This cyclecan be repeated as necessary to produce a smooth and uniform tungstennucleation layer with the desired thickness

The Method

According to the methods of the invention, a first wafer orsemiconductor substrate is placed into the deposition or reactionchamber and onto a station which has been heated to betweenapproximately 250 and 475° C., and preferably between about 250 and 350°C. Prior to the pulsed nucleation process, the semiconductor substrate,optionally, has been exposed to a gas which promotes growth of tungstenwith no delays. This step, which is called an initiation soak step,comprises exposure of the substrate to a gas such as SiH₄, B₂H₆, Si₂H₆,H₂, Ar, N₂, or O₂, or a combination thereof, in a gaseous or plasmastate for about 2 to about 60 seconds. The plasma state can be producedusing a radiofrequency or microwave energy source. This serves toprecondition the substrate surface.

Any reducing agents such as SiH₄, B₂H₆, Si₂H₆, SiH₂Cl₂, or H₂, or acombination thereof, could be used for the pulsed nucleation process.Preferably, the reducing gas will comprise SiH₄ along with an inertcarrier gas. The reducing gas is supplied at flow rates of approximately400 to about 220, and more preferably, at about 100 to about 200, andmost preferably about 200 standard cubic centimeters per second (sccm).This flow is continued for a predetermined time, typically about 5seconds or less and preferably, about 2 seconds, and the flow ofreducing gases is stopped. Generally, a gas line charge time of about0.5 seconds is used to pressurize the gas flow lines leading to thedeposition chamber prior to release of the gas into the chamber. Uponcompletion of the reducing gas flow time in the chamber, the gas line tothe chamber is closed and then evacuated for about 0.5 seconds byutilization of a rough pump line. This is the gas line purge time. Theline charge and purge times of the reducing gas can be overlapped withthe chamber purge times

The reaction chamber is purged prior to beginning the flow of thetungsten-containing gases. Purging preferably is accomplished byintroduction of an inert gas, or nitrogen, or hydrogen, or a mixturethereof into the deposition chamber at fixed pressure and/or the vaporphase in the deposition chamber is removed through the application of alow pressure vacuum, preferably using a fast pump.

Any tungsten-containing gas, including but not limited to, WF₆, WCl₆, orW(CO)₆ can be used for the pulsed nucleation process. Preferably, thetungsten-containing gas comprises WF₆ along with an inert carrier gas.Typically, the tungsten-containing gas flow rate is betweenapproximately 200 to about 900 sccm; preferably, between about 200 and800 sccm, and most preferably, at about 600 sccm. It has been found thattungsten deposition occurs only on the surface where reducing gas hasbeen absorbed. This flow is continued for a predetermined time,typically about 5 seconds or less and preferably, about 2 seconds, andthe flow of reducing gases is stopped. Generally, a line charge of about0.5 seconds is used. Upon completion of the tungsten-containing gas flowtime in the chamber, the gas line to the chamber is closed and thenevacuated for about 0.5 seconds by utilization of a rough pump line.This is the gas line purge time. The line charge and purge times of thetungsten-containing gas can be overlapped with the chamber purge times.

It will be understood that an inert gas such as argon or another gassuch as nitrogen or hydrogen, or a combination thereof may be providedas the background gas to the deposition station simultaneously with thereducing gases or the tungsten-containing gases. In general, the flow ofthe background gases are continuous, i.e., it is not switched on and offas are the tungsten-containing gas and the reducing gas.

Using the methods described herein, the growth rate of tungsten percycle is between about 8 and 12 Angstroms, and preferably between about10 and 12 Angstroms per cycle as compared to a growth rate of less than2.5 A that can be achieved using the conventional ALD processes.

The Product

The present invention provides a method for forming seed layers incontacts or vias with improved step coverage. More specifically, usingthe methods described herein, nucleation layers having a step coverageof greater than 75%; preferably, greater than 80%; and more preferably,greater than 90% can be achieved. In addition, this level of stepcoverage can be repeatedly and routinely produced in even high aspectratio contacts, including, but not limited to contacts have an aspectratio of greater than 10:1, or even 13:1 or greater.

Panel A of FIG. 1 illustrates the relationship between nucleation layerfilm thickness and number of cycles. Panel B of FIG. 1 shows therelationship between growth rate and number of cycles. The depositionswere done at a substrate temperature of between 250 and 350° C. Asshown, the nucleation layers will generally have a thickness of greaterthan about 50 Angstroms; and preferably, between about 80 and about 100Angstroms.

As shown in FIG. 2, the pulsed nucleation layers produced by the methodsdescribed herein are substantially less rough and have a smaller grainsize, as measure by atomic force microscopy, than tungsten filmsproduced by conventional CVD.

Subsequent Process Steps

According to aspect of the invention, the pulsed nucleation cycledescribed above can be repeated until a near-continuous, e.g., >50%,nucleation layer is formed. Subsequent cycles optionally are performedwith continuous hydrogen gas flow in connection with the alternatingpulses of reducing and tungsten-containing gases. Preferably, about fourto ten cycles of the pulsed nucleation are performed prior to the use ofhydrogen with the tungsten-containing gases. As shown in FIG. 3, the useof continuous hydrogen results in an increase in growth rate and thus, areduction of the number of cycles required to form the nucleation layer.A representative tungsten nucleation layer of 100 Angstroms thicknesswith step coverage of 96% in contacts with an aspect ratio of 12:1 canbe produced as follows:

SiH₄  200 sccm for 2 seconds WF₆  600 sccm for 2 seconds Hydrogen 7000sccm Argon 7000 sccm Preheat 30 seconds 5 cycles, 42 seconds at 350° C.

According to another aspect of the invention, the purging step betweenthe alternating tungsten and reducing agent dosing is performed byintroducing hydrogen or nitrogen gas into the deposition chamber.

According to another aspect of the invention, the pulsed nucleationprocess is followed by more conventional bulk processing using H₂ and/orSiH₄ with WF₆ (or another tungsten-containing gas) in a CVD process.Thus, the methods of the invention can further comprise the step ofdepositing tungsten film by CVD atop the nucleation layer by contactingthe nucleation layer with SiH₄ and/or H₂ simultaneously with WF₆ undersuitable conditions to deposit a tungsten film.

Furthermore, a soak step could be implemented subsequent to the pulsednucleation process and prior to the CVD process as described above. Thesoak step can comprise of substrate exposure to gases such as N₂, H₂,O₂, Si₂H₆, B₂H₆, or a combination thereof in a gaseous or plasma state.

If a multi-station reactor that enables parallel processing of multiplewafers is used, the alternating reactant deposition process may occur onsome stations, simultaneous WF₆—SiH₄ CVD on other stations aftercompletion of alternating deposition process, and then simultaneousWF₆—H₂ CVD on the final deposition stations for complete tungsten fill.

More specifically, wafers that had been subjected to the pulsedalternating deposition methods described herein at the first 1, 2, 3, ormore stations of the multi-station deposition system are then moved to astation wherein tungsten is deposited by the reaction of WF₆ and H₂. TheWF₆ and H₂ gases are simultaneously introduced to achieve excellentgap-fill by chemical vapor deposition at higher rates. In addition,inert gases can also be flowed to the deposition stations. When such amulti-station system is used, the deposition temperatures can beindependently optimized for the alternating-process deposition describedherein or for subsequent steps involving WF₆—SiH₄ CVD and/or WF₆—H₂ CVD.This process can be formed on some but not all of the pedestals of themulti-station system with hydrogen and WF₆ gases flowing simultaneouslyonto the other pedestals.

As one of skill will appreciate, this process can be performed withcontinuous hydrogen and/or nitrogen flow during both dosing and purging

As one of skill may appreciate, it may be advantageous to have anadditional SiH₄ dose step after the final dosing with thetungsten-containing gases to protect subsequent layers from residualtungsten residue in the chamber.

According to another aspect of the invention, the pulsed nucleationlayers of the invention can serve as a seed layer for subsequentdeposition of Cu or other metals. Likewise, formation of the pulsednucleation layer can be followed by preparation of a barrier layer. Forexample, the methods of the invention can further comprise the step ofdepositing a tungsten barrier film by CVD atop the nucleation layer bycontacting the nucleation layer with diborane, and optionally silane,simultaneously with WF₆ under suitable conditions to deposit thetungsten film.

Further, it will be recognized by those skilled in the art that avariety of techniques of forming interconnect, such as the single ordual damascene technique, or other traditional techniques of forming lowresistance contacts or plugs which involve filling an opening withconductive materials such as tungsten or aluminum may be used topractice the present invention. Moreover, it should be understood thatthe present invention is applicable to forming a seed layer in a contactand/or a via atop a conductive or a doped region formed on asemiconductor substrate.

Deposition Chamber

The methods of the invention may be carried out in a Novellus Altus CVDchamber, the Concept 2 Altus chamber, the Concept 3 Altus processingchamber, or any of a variety of other commercially available CVD tools.More specifically, the process can be performed on multiple depositionstations in parallel. See, e.g., U.S. Pat. No. 6,143,082, which isincorporated herein by reference for all purposes. In some embodimentsof the present invention, the pulsed nucleation process is performed ata first station that is one of five or more deposition stationspositioned within a single deposition chamber. Thus, the reducing gasesand the tungsten-containing gases are alternately introduced to thesurface of the semiconductor substrate, at the first station, using anindividual gas supply system that creates a localized atmosphere at thesubstrate surface. After nucleation of the tungsten film is complete,the gases are turned off. The semiconductor substrate, having a firstthickness of tungsten deposited at a first rate, is then moved to asecond deposition station and a new wafer is moved into place on thefirst station. The wafers may be indexed from one deposition station tothe next to enable parallel wafer processing after one or morerepetitions of the cycle. The full thickness of the tungsten film isachieved by additional cycles with alternating reducing gases andtungsten-containing gases at one or more of the other depositionstations. This is repeated until all substrates are coated to thedesired thickness. It is the sum of these individual depositions thatforms the total amount of W nucleation layer deposited. Any number ofdeposition stations, each capable of having a localized atmosphereisolated from adjacent stations, is possible within the single chamber.

The invention also provides for a deposition chamber in whichalternating deposition stations are dedicated to deliver eithertungsten-containing gases or reducing gases. More specifically, thedeposition stations in the chamber are separated into two groups withthe first group dedicated to delivery of the reducing gases and thesecond group for introducing tungsten containing gas. These stationsalso can provide for the simultaneous delivery of inert gases with thededicated gases. Thus, tungsten is deposited by moving wafers fromstation to station such that the wafer is sequentially exposed to thereducing gases and then the tungsten-containing gases until the desiredthickness of tungsten is obtained.

Another aspect of the invention provides for a module for alternatingdeposition of tungsten containing one or more of the following designelements:

-   a plurality of deposition stations comprising a showerhead or    dispersion plate for uniform gas introduction paired with a heated    pedestal that holds a wafer underneath the showerhead;-   a plurality of deposition stations with showerheads flush-mounted    with the top of the module vacuum chamber to minimize gas    re-circulation in the module and promote efficient purging between    alternating deposition steps;-   a fully purged top plate of the module vacuum chamber consisting of    a purge gas plenum covering the top plate area not occupied by    deposition showerheads wherein improved station-to-station isolation    and reduced purge times between deposition cycles are obtained; or-   a vacuum chamber in which the heated pedestals from each deposition    station are completely or partially isolated from each other by an    annular pumping ring connected to the chamber exhaust. This feature    further enhances station-to-station isolation and enables different    processes to be run simultaneously on alternate stations in the same    module.

The module may further comprise means, provided to each showerhead, forcreating a RF plasma in between the showerheads and the substrateplatens. Preferably, such means comprise an RF energy source, a matchnetwork, and the necessary electrical connections. In anotherembodiment, the module may further comprise means for creating amicrowave plasma in the chamber.

A representative example of such a module having a flush-mountedshowerhead, a fully purged top plate, and an annular pumping port isshown in FIG. 5.

As will be appreciated in the art, each such deposition station willtypically have a heated substrate platen for holding and heating asubstrate to a predetermined temperature. In addition, each typicallywill have a backside gas distribution system to prevent deposition ofthe W film on the backside of the substrate, and a vacuum clampingmanifold for clamping the substrate to the platen. Finally, thedeposition chamber can be equipped with a transport system fortransporting wafers or substrates into and out of the chamber as well asbetween deposition stations.

The invention also provides for a gas manifold system which may be usedto provide line charges to the various gas distribution lines as shownschematically in FIG. 4. Manifold 104 has an input 102 from a source ofthe tungsten-containing gas (not shown), and manifold 204 has an input202 from a source of the reducing gas (not shown). The manifolds, 104and 204, provide the tungsten-containing gas and reducing gases to thedeposition chamber through valved distribution lines, 105 and 205,respectively. The various valves are opened or closed to provide a linecharge, i.e., to pressurize the distribution lines. More specifically,to pressurize distribution line 105, valve 106 is closed to vacuum andvalves 108 is closed. After a suitable increment of time, valve 108 isopened (valve 208 is closed) and the tungsten-containing gas isdelivered to the chamber. Again, after a suitable time for delivery ofthe gas, valve 108 is closed. The chamber can then be purged to a vacuumby opening of valves 106 to vacuum.

A similar process is used to deliver the reducing gas. For example, theline is charged by closing valve 208 and closing valve 206 to vacuum.Opening of valve 208 allows for delivery of the reducing gas to thechamber. It has been found that the amount of time allowed for linecharges changes the amount and timing of the initial delivery of thegas.

FIG. 4 also shows vacuum pumps wherein valves 106 and 206, respectively,can be opened to purge the system. The supply of gas through the variousdistribution lines is controlled by a controller, such as a mass flowcontroller which is controlled by a microprocessor, a digital signalprocessor or the like, that is programmed with the flow rates, durationof the flow, and the sequencing of the processes.

It is understood that the examples and embodiments described herein arefor illustrative purposes only and that various modifications or changesin light thereof will be suggested to persons skilled in the art and areto be included within the spirit and purview of this application andscope of the appended claims. All publications, patents, and patentapplications cited herein are hereby incorporated by reference in theirentirety.

What is claimed is:
 1. A method of forming a tungsten nucleation layer asurface of a semiconductor substrate comprising the steps of:positioning said semiconductor substrate at a deposition station withina deposition chamber; performing an initiation soak step, comprisingexposure of the substrate to a gas in a gaseous or plasma state; afterthe initiation soak step, flowing a reducing gas into said depositionchamber whereby about one or more monolayers of reducing gas aredeposited onto said surface of said substrate; purging the reducing gasfrom the deposition chamber; and flowing a tungsten-containing gas intosaid deposition chamber, whereby deposited reducing gas is replaced bytungsten to provide said nucleation layer in a surface controlleddeposition process.
 2. The method of claim 1, wherein said initiationsoak gas comprises SiH₄, B₂H₆, Si₂H₆, H₂, Ar, N₂, or O₂, or acombination thereof.
 3. The method of claim 1, wherein said initiationsoak gas is in a plasma state which is produced by either anradiofrequency or microwave energy source.
 4. The method of claim 1,wherein said reducing gas comprises SiH₄, Si₂H₆, H₂. B₂H₆, SiH₂Cl₂ or acombination thereof.
 5. The method of claim 1, wherein saidtungsten-containing gas comprises WF₆, WCl₆, or W(CO)₆.
 6. The method ofclaim 1, wherein said reducing gas further comprises argon, hydrogen,nitrogen, or a combination thereof.
 7. The method of claim 1, whereinsaid tungsten-containing gas further comprises argon, hydrogen,nitrogen, or a combination thereof.
 8. The method of claim 1, furthercomprising the step of purging said tungsten-containing gas.
 9. Themethod of claim 8, wherein the steps are repeated to complete depositionof the tungsten nucleation layer.
 10. The method of claim 8, whereinsaid purging further comprises introducing a purge gas at a fixedpressure.
 11. The method of claim 10, wherein said purge gas ishydrogen, nitrogen, an inert gas, or a mixture thereof.
 12. The methodof claim 8, wherein said purging further comprises evacuating gases fromthe chamber.
 13. The method of claim 1, further comprising: treatingsaid substrate with SiH₄, Si₂H₆, B₂H₆, N₂, O₂, H₂, an inert gas, or acombination thereof in a gaseous or plasma state.
 14. The method ofclaim 1, wherein said deposition chamber has a single station.
 15. Themethod of claim 1, wherein said deposition chamber has multiplestations.
 16. The method of claim 15, further comprising: repositioningsaid semiconductor substrate to a second deposition station; providing asecond reducing gas to said surface; and providing a secondtungsten-containing gas to said surface to provide a second tungstenfilm, wherein said second tungsten film is at least about one monolayerthick.
 17. The method of claim 15, wherein one or more stations is usedfor pulsed nucleation to form the seed layer and the remainder of thestations are used for CVD plugfill.
 18. The method of claim 17, furthercomprising: repositioning said semiconductor substrate to a seconddeposition station, wherein said substrate has a nucleation layer of thedesired thickness; and contacting the substrate with a WF₆ and areducing gas under CVD conditions.
 19. The method of claim 15, whereinthe substrate is preheated at a first station and then repositioned to asecond station for said initiation soak step.
 20. The method of claim15, wherein after the initiation soak step, the substrate isrepositioned to a second deposition station.
 21. A method of forming atungsten film on a surface of a substrate in a deposition chamber, themethod comprising: (a) prior to forming any tungsten on the substratesurface, exposing the surface to an initial dose of a boron-containingcompound; (b) exposing the substrate to a tungsten-containing gas thatis reduced to form a first portion of a tungsten nucleation layer on thesubstrate; (c) after forming the first portion of the tungstennucleation layer, contacting the substrate with a silane; (d) exposingthe tungsten-containing gas to thereby reduce the tungsten-containinggas to form another portion of the tungsten nucleation layer on thesemiconductor substrate.
 22. The method of claim 21, wherein thesubstrate temperature is between about 250° C. to 350° C.
 23. The methodof claim 21, further comprising depositing a bulk tungsten layer on thetungsten nucleation layer by contacting the substrate with atungsten-containing gas and hydrogen under chemical vapor deposition(CVD) conditions.
 24. The method of claim 21, wherein the depositionchamber has a single station.
 25. The method of claim 21, wherein thedeposition chamber has multiple stations.
 26. The method of claim 21,wherein the boron-containing compound is diborane.
 27. The method ofclaim 26, wherein the silane compound is silane or disilane.